WO2015140062A1 - Procédé et dispositif pour la séparation d'une substance présente dans une solution - Google Patents

Procédé et dispositif pour la séparation d'une substance présente dans une solution Download PDF

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Publication number
WO2015140062A1
WO2015140062A1 PCT/EP2015/055279 EP2015055279W WO2015140062A1 WO 2015140062 A1 WO2015140062 A1 WO 2015140062A1 EP 2015055279 W EP2015055279 W EP 2015055279W WO 2015140062 A1 WO2015140062 A1 WO 2015140062A1
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Prior art keywords
solution
intensity
crystallization
formula
temperature
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PCT/EP2015/055279
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German (de)
English (en)
Inventor
Matthias Rauls
Hans Ziegler
Martin Haubner
Original Assignee
Basf Se
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Publication date
Application filed by Basf Se filed Critical Basf Se
Priority to MX2016012125A priority Critical patent/MX2016012125A/es
Priority to JP2016557950A priority patent/JP6702880B2/ja
Priority to ES15709501T priority patent/ES2898659T3/es
Priority to EP15709501.9A priority patent/EP3119489B1/fr
Priority to PL15709501T priority patent/PL3119489T3/pl
Priority to CN201580014534.2A priority patent/CN106132496B/zh
Priority to EP21181477.7A priority patent/EP3919148B1/fr
Priority to US15/127,135 priority patent/US10294182B2/en
Publication of WO2015140062A1 publication Critical patent/WO2015140062A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/0018—Evaporation of components of the mixture to be separated
    • B01D9/0031—Evaporation of components of the mixture to be separated by heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/10—Vacuum distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/0004—Crystallisation cooling by heat exchange
    • B01D9/0013—Crystallisation cooling by heat exchange by indirect heat exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/0036—Crystallisation on to a bed of product crystals; Seeding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/0063—Control or regulation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/0077—Screening for crystallisation conditions or for crystal forms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by isomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C07F5/069—Aluminium compounds without C-aluminium linkages
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/47—Scattering, i.e. diffuse reflection
    • G01N21/49—Scattering, i.e. diffuse reflection within a body or fluid
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84—Systems specially adapted for particular applications
    • G01N21/85—Investigating moving fluids or granular solids
    • G01N21/8507—Probe photometers, i.e. with optical measuring part dipped into fluid sample
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84—Systems specially adapted for particular applications
    • G01N2021/8405—Application to two-phase or mixed materials, e.g. gas dissolved in liquids

Definitions

  • the present invention relates to a method for separating a substance from a solution. The separation takes place via a crystallization process. Furthermore, the invention relates to a process for working up an aluminum-containing
  • Citronellal in the presence of complex compounds comprising at least one ligand of the formula (I):
  • the invention relates to a process for the preparation of isopulegol and a process for the preparation of menthol.
  • Menthol is the world's most important aroma chemical. The demand for menthol is still largely covered by isolation from natural sources. However, there are also synthetic approaches to menthol, partly in racemic form, partly in the form of the natural enantiomer L-menthol.
  • isopulegol which is usually prepared by cyclizing oxo-ene reaction of citronellal in the presence of Lewis acidic catalysts and thereby usually in the form of mixtures of the four diastereomers isopulegol, iso - Obtains isopulegol, neo-isopulegol and neoiso-isopulegol.
  • Suitable catalysts for carrying out the above-mentioned cyclization of citronellal to isopulegol both heterogeneous catalysts, such as S1O2, AI2O3 / S1O2-, Si0 2 / Zr0 2 were -, Si02 / Ti0 2 -Mischkatalysatoren, mordenites, faujasites,
  • WO 2006/092433 A1 describes bis (diarylphenoxy) -aluminum compounds obtainable by reacting a bis (diarylphenol) ligand of the formula (I) with a suitable aluminum compound, as well as processes for the preparation of isopulegol and menthol in the presence of these Links. In this case, methods are disclosed which provide a recovery of the used
  • WO 2008/025851 A1 discloses a process for working up an aluminum-containing reaction product from the preparation of isopulegol by cyclization of citronellal, in which the reaction product is subjected to a distillative separation to give an isopulegol-enriched top product and an isopulegol-depleted bottom product and separating the ligand from the bottom product. Furthermore, from WO 2009/068444 A2 a process for the preparation of menthol is known in which neral and / or geranial is hydrogenated catalytically to citronellal and citronellal is cyclized to isopulegol in the presence of an acidic catalyst. Isopulegol is then purified by crystallization and catalytically hydrogenated to menthol.
  • the present invention is therefore an object of the invention to provide a method and an apparatus of the type mentioned, in which a better efficiency in the crystallization process is achieved, which in the context of the method for separating a substance or in the device for separating the Stoffes is used. In addition, the time required to recover the substance should be shortened.
  • this object is achieved by a method having the feature of claim 1 and a device having the feature of claim 18.
  • electromagnetic radiation is radiated into the solution.
  • An intensity of the electromagnetic radiation scattered by crystals in the solution is detected, and the detected intensity is compared with a target intensity.
  • the temperature of the solution is then controlled in dependence on the difference of the detected intensity and the target intensity so that the amount of this difference decreases.
  • Crystallization process started in which crystals of the substance are recovered, which are then separated.
  • a solution is understood in this document not only a clear solution in which all solids are dissolved, but also a particle-laden solution. Such a particle-laden solution is also referred to as a suspension.
  • a particle-laden solution may contain crystals that have formed during crystallization. During crystallization, a transition from a clear solution to a solution may take place
  • solution in this particular case can stand for both a “clear” solution and a particle-laden solution (suspension).
  • the detected intensity does not include all the electromagnetic radiation scattered by the crystals in the solution, but only a part of this total scattering intensity, in particular only a proportion proportional to this total scattering intensity.
  • the detected intensity does not include all the electromagnetic radiation scattered by the crystals in the solution, but only a part of this total scattering intensity, in particular only a proportion proportional to this total scattering intensity.
  • the change in the crystal surface can be detected sufficiently to control the temperature for the beginning of the crystallization process.
  • Filter resistance and the duration of the filtration or alternatively to be provided filter surfaces results in that the filtration on the available apparatus or in the time available is impossible if the exact amount of seed crystal is missed at the beginning of the crystallization process.
  • Crystallization process is present in order to achieve an ideal crystal size and morphology for the separation of the crystals by means of the crystallization process.
  • the saturation temperatures of the solution submitted in a wide range for example between 85 ° C to 1 15 ° C vary.
  • the method according to the invention makes it possible, in spite of the uncertainties resulting from the process, to provide a simple, automatable regulation of the correct inoculation.
  • Difficulty could be reduced by a cascading, in which several crystallizers are operated at only slightly different temperature levels.
  • the necessity of numerous temperature stages and thus a large number of apparatus makes this process economically disadvantageous.
  • Such a measurement may be inline e.g. done with spectroscopic methods or done offline in a chemical laboratory. The latter method, however, means too much time; It fails like the spectroscopic measurement but even if a very complex composition of the solution is present.
  • composition has an effect on the exact dissolution temperature. It is important to measure the exact concentration of all the other components of the solution which, like isopulegol, can greatly increase the solubility or, like the substance group termed "ester”, greatly reduce their solubility the concentration of all components and the settling saturation temperature, which can not be achieved for a complex composite medium.
  • Determination of the saturation temperature may be a way out. For example, one can see the saturation temperature of such a solution by deliberate supercooling of the solution, forcing the crystal formation at u.U. high supercooling and reheating of the solution to determine the dissolution temperature of the last crystal. This process can also be laboriously carried out on a sample in the laboratory; It is also conceivable to perform this measurement automatically by any measuring system in the bypass to the actual crystallizer. With a high supercoolability of the solution and because of the need to heat the solution very slowly to accurately determine the saturation temperature, such a determination would take at least many hours and would thus be economically disadvantageous.
  • Measuring method used in conjunction with a control of the initial conditions for the crystallization process used in the process This electromagnetic radiation is radiated into the solution and that of about
  • radiated electromagnetic radiation are, to a first approximation proportional to the amount of crystal surface present in the suspension.
  • the method according to the invention thus does not detect the mass of crystals at the beginning of the crystallization process, but rather the crystal surface.
  • an even better crystal growth and thus an even higher yield and less time spent in the separation of the crystals can be achieved, since not the mass of crystals for the success of the crystallization is important, but the ready for absorbing supersaturation crystal surface.
  • the measurement of the crystals by means of the electromagnetic radiation for controlling the conditions at the beginning of the crystallization process is particularly advantageous.
  • the limit value for the magnitude of the difference of the detected intensity and the desired intensity is a tolerated deviation from the desired intensity. This limit may be, for example, 5% or 20% of the target intensity. Of the However, limit can also be determined on the basis of absolute deviations from the target intensity. If the target value z. B. at 0.1 so you could choose the target range of 0.15 to 0.1. If the target value is 0.5, the target range would be 0.55 to 0.5.
  • the crystalline substance is separated by filtration.
  • a target intensity was chosen which was a
  • the desired intensity is determined by reference measurements. For these reference measurements, the relationship between crystal size and / or crystal morphology at the end of the crystallization process and the intensity detected at the beginning of the crystallization process is determined for the solution. From this, the desired intensity is selected as the intensity which is assigned to the desired crystal size and / or crystal morphology.
  • Electromagnetic radiation can thus be controlled in the inventive method, the temperature for the beginning of the crystallization process.
  • the solution or a part of the solution in a crystallization vessel is brought to a temperature which is lower than a defined initial temperature value which is below that
  • the solution then becomes heated until the amount of the difference of the detected intensity and the target intensity is smaller than the limit value.
  • the solution is brought to a temperature far below the anticipated saturation temperature, so that spontaneously a large number of crystals of the substance to be crystallized form. In this way, seed crystals are obtained in situ.
  • the method according to the invention thus regulates the temperature of the solution from lower to higher temperatures in order to obtain an ideal starting temperature for the crystallization process.
  • this scheme is the existing
  • the crystal size and morphology does not match the desired crystal size and morphology.
  • the initial temperature value is in particular at least 10 K below the anticipated saturation temperature of the solution.
  • Initial temperature value can also be determined from the desired intensity.
  • the initial intensity associated with the initial temperature value is chosen to be the x-fold intensity of the desired intensity, with the value x ranging from 1.2 to 10.
  • the value x is in a range from 3 to 10, preferably in a range from 4 to 9 and particularly preferably in a range from 6 to 9. Die
  • the temperature of the solution is then adjusted until the detected intensity is greater than the initial intensity.
  • Crystallization process particularly critical to the formation of crystals that are suitable for later filtration. In these cases, it is therefore particularly important that the initial conditions, ie in particular the crystal surface to Beginning of the crystallization process, ideal for crystal growth during the crystallization process. With the method according to the invention, it can be ensured by the irradiation of the electromagnetic radiation and the measurement of the intensity of the backscattered radiation that ideal conditions exist at the beginning of the crystallization.
  • Wavelength ranges wider than 20 nm are radiated into the solution larger than 20 nm.
  • the irradiated electromagnetic radiation thus comprises different wavelengths which extend at least over a range of 20 nm. In particular, it does not become monochromatic light or monochromatic radiation, as in the case of laser radiation. Radiation in a very narrow frequency range, but light or radiation of different wavelengths. In particular, the wavelength range can also be much wider and be more than 50 nm, 100 nm or more nm
  • the electromagnetic radiation radiated into the solution or suspension has the form of a jet.
  • the minimum cross section of this beam is greater than 0.1 mm
  • the beam is particularly divergent, i. he has an opening angle. This opening angle is e.g. greater than 5 °, in particular greater than 10 ° and preferably greater than 20 °. Since the cross section of such a divergent beam in
  • the irradiated electromagnetic radiation may be in the visible spectral range, for example.
  • infrared radiation is radiated into the solution.
  • the intensity of infrared radiation is detected.
  • the infrared radiation may be, for example, in a wavelength range from 780 nm to 1000 nm, in particular in a range from 800 nm to 900 nm and preferably in a range from 820 nm to 880 nm.
  • the wavelength of the irradiated electromagnetic radiation corresponds to the wavelength of the detected, backscattered radiation.
  • the electromagnetic radiation is irradiated into the solution by means of a scattered light probe.
  • the intensity of the backscattered electromagnetic radiation is detected by means of the scattered light probe.
  • the direction of irradiation of the irradiated electromagnetic radiation is substantially parallel to the detection direction, from which the intensity of the backscattered electromagnetic radiation is detected. In this way it is prevented that radiated into the solution electromagnetic radiation is detected directly, without that radiation has been scattered on crystals.
  • a signal can be obtained by the above-characterized irradiation of the electromagnetic radiation into the solution or suspension, in particular by means of a scattered light probe, by detecting the intensity of the electromagnetic radiation scattered by crystals in the solution or suspension that is proportional to
  • Crystallization be set very precisely, as this can be detected very accurately the initially available amount of seed crystals.
  • the inventive method has significant advantages over a measurement of the particle size distribution and the number of particles, as they
  • FBRM focused beam reflectance measurement
  • the particle size distribution is not determined directly, but via a so-called chord length distribution.
  • a laser beam is irradiated into the solution with the particles.
  • the laser beam has a very small cross-section of a few microns. It also rotates at a constant speed of about 2 m / s. Particles hit by the rotating laser beam are scanned in this way.
  • Measured is the electromagnetic radiation, which are detected by reflection of the laser beam to the particles from a sensor. From the given rotational speed, with which the laser beam is moved, and the pulse durations, chord length distributions are then calculated.
  • chord length distributions are then calculated.
  • Minimum slope is set as a parameter to a very low value, more distant particles can not be detected because the
  • Signal processing electronics to a high cutoff frequency is designed to ensure a high temporal resolution of the signal.
  • electromagnetic radiation has the above-mentioned features, this radiation is generated in particular by a so-called scattered light probe, the surface of particle collectives can be measured in suspensions with a very low to a very high number of particles per volume. It is possible to use only the intensity, i. in particular the total intensity, the
  • the FBRM method no direct intensity measurement is made carried out. Namely, in this method, the gain of the signal processing electronics is set differently for each type of particle so that neither too high nor too low a signal is detected. In fact, the FBRM method depends only on the number and duration of the light pulses resulting from the reflection on the particles, but never on the intensity of the reflected radiation.
  • Measuring method by means of the scattered light probe or by means of electromagnetic radiation which has the aforementioned characteristics, better suited than the FBRM method, since it has a higher sensitivity. Besides, it is very much
  • the solution (suspension) is introduced into a crystallization vessel at a temperature which is below the initial temperature value.
  • the introduced solution thus has a large amount of crystal. If the scattered light probe is within the introduced solution, i. If the crystallization vessel is filled so far that the level of the solution above the scattered light probe, the electromagnetic radiation is radiated by means of the scattered light probe in the solution and the intensity of the
  • the temperature of the solution is controlled during the further introduction of the solution into the crystallization vessel so that the amount of the difference of the detected intensity and the target intensity becomes smaller than the limit value.
  • the detected intensity equal to the desired intensity or the amount of the difference of these intensities is smaller than the limit value, so that at full filling of the
  • Crystallization vessel the desired Impfkristallmenge is present.
  • the amount of the difference of the detected intensity and the target intensity is still greater than the limit value, the detected intensity of the target intensity can be so far approximated by a fine adjustment of the temperature that the amount of the difference is below the limit value and thus then the desired amount of seed crystal is present.
  • the method of separating the substance from the solution is used as the part of the method that begins when the amount of the difference in the detected intensity and the target intensity is less than a limit, although in previous parts of the method itself Crystals have formed.
  • the crystallization process which is used in the context of the inventive method for separating the substance from the solution, it is in particular a cooling crystallization process.
  • the solution is slowly cooled again, so that, supported by the in situ obtained seed crystals, larger again Form crystals.
  • the cooling rate is initially relatively low, later, if already larger crystals have formed, the cooling rate can also
  • the invention further relates to a method for recovering a substance from a solution by means of crystallization, in which the solution in a first
  • Crystallization vessel is introduced and the substance is separated by means of crystallization in the first crystallization vessel according to the method described above. While performing the crystallization process in the first
  • Crystallization vessel the solution is introduced into a second crystallization vessel and the substance separated by means of crystallization in the second crystallization vessel according to the method described above.
  • Crystallization vessel started from the front.
  • the process for separating the substance from the solution can be operated essentially continuously, since during the crystallization in one crystallization vessel the solution is introduced into the other crystallization vessel and the regulation is carried out to achieve the desired crystal surface for the beginning of the crystallization process in the second crystallization vessel.
  • even more crystallization vessels can be connected in parallel. The number of crystallization vessels depends, for example, on how much time needed to get the desired initial conditions for the
  • the number of crystallization vessels can be selected, for example, such that solution is introduced into crystallization vessels until the crystallization process in the first crystallization vessel has been completed and the solution can be introduced thereinto again.
  • the invention further relates to a device for separating a substance from a solution.
  • the device has at least one crystallization vessel, which comprises an opening for introducing the solution.
  • the device comprises a tempering device for changing the temperature of the solution to be introduced and / or introduced.
  • a temperature sensor is provided for measuring the temperature of the solution to be introduced and / or introduced.
  • a scattered light probe is arranged, with which electromagnetic radiation can be irradiated into the solution and an intensity of the electromagnetic radiation is detected, which was scattered by crystals in the solution.
  • the device further comprises a control unit, which is coupled with the temperature sensor, the scattered light probe and the tempering device in terms of data technology.
  • the temperature of the solution in the crystallization vessel is adjustable so that the amount of the difference of the detected intensity and a desired intensity decreases. If the amount of the difference of the detected intensity and the target intensity is smaller than a limit value, a crystallization method can be controlled. The crystallization process produces crystals of the substance. Finally, the device comprises a separation unit for separating the crystals obtained.
  • the tempering device is arranged in particular in the line, via which the solution is fed to the crystallization vessel. In this way, the temperature of the supplied solution can be controlled.
  • the temperature sensor is arranged in particular in the crystallization vessel, so that the temperature of the solution located in the crystallization vessel is measured.
  • a temperature sensor is also provided in the line, via which the solution is fed to the crystallization vessel.
  • the scattered light probe has an emitter for infrared radiation.
  • the radiation emitted by the emitter is transmitted through a waveguide into the Conducted crystallizer.
  • the decoupling surface of the waveguide is arranged in the lower region of the crystallization vessel, so that, as of a certain level, electromagnetic radiation is radiated into the solution.
  • the scattered light probe in particular has a coupling-in surface of a further waveguide in the crystallization vessel.
  • the scattered light coupled in via the coupling surface is conducted via the further waveguide to a detector of the scattered light probe.
  • the electromagnetic radiation radiated by the scattered light probe lies in one
  • Wavelength range or multiple wavelength ranges that is wider than 20 nm.
  • the wavelength range or the wavelength ranges may in particular also be wider than 50 nm or 100 nm.
  • the beam which can be generated by the scattered light probe has a minimum cross section which is greater than 0.1 mm, in particular greater than 0.39 mm.
  • the beam preferably has one
  • Opening angle which is greater than 5 °, preferably greater than 10 ° and in particular greater than 20 °.
  • the separation unit is so
  • the device according to the invention is in particular designed to carry out the method according to the invention described above. It thus has the same advantages as the method. According to a development of the device according to the invention, this comprises two crystallization vessels. For both crystallization vessels, a tempering device, a temperature sensor and a scattered light probe are provided in this case. The control unit controls in this case the solvent supply so that during the implementation of the crystallization process in the first crystallization vessel, the solution is introduced into the second crystallization vessel and then the crystallization process is then carried out in the second crystallization vessel.
  • the present invention further provides a method for
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 are independently selected from C6-C15-
  • Aryl radicals or C 2 -C 20 -heteroaryl radicals which may each have 1 to 7 identical or different substituents selected from C 1 -C 6 -alkyl, C 1 -C 6 -perfluoroalkyl, C 1 -C 6 -alkoxy, C 7 -C 12 -aralkyl, halogen, SiR 5a R 6a R 7a , optionally substituted C 6 -Cio-aryl, NR 8a R 9a , SR 10a , N0 2 may mean
  • R 1 , R 2 , R 3 , R 4 are independently selected from hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -perfluoroalkyl, C 1 -C 6 -alkoxy, C 7 -C 12 -aralkyl, halogen, SiR 5b R 6b R 7b , optionally substituted C 6 -C 10 aryl, NR 8b R 9b , SR 10 ,
  • R 1 or R 2 and / or R 3 or R 4 together with A can form an aromatic or non-aromatic cycle, mean and
  • A is a straight-chain or branched and / or cyclic
  • Hydrocarbon radical having 1 to 25 carbon atoms which may be saturated or mono- or polyunsaturated and / or partially aromatic and optionally one or more identical or different heteroatoms selected from O, S, NR 11 , and / or one or more identical or different functional groups selected from the functional groups C (O), S (O), S (0) 2, and optionally one or more identical or different substituents selected from the substituents Ci-C6-alkyl, C1 -C6-perfluoroalkyl, Ci-C6-alkoxy, Ci-Cio-acyloxy, C7-Ci2-aralkyl, halogen, -
  • SiR 5c R 6c R 7c optionally substituted C6-Cio-aryl, substituted or unsubstituted C 2 -Cio-hetaryl, NR 8c R 9c , SR 10c , N0 2 , Ci-Ci 2 acyl, C 1 -C 10 carboxyl, or is a C 6 -C 15 aryl radical or a C 2 -C 15 heteroaryl radical optionally each 1 to 5 substituents selected from C 1 -C 6 -alkyl, C 1 -C 6 -fluoroalkyl, C 1 -C 6 -alkoxy, C 7 -C 2 -aralkyl, halogen, SiR 5d R 6d R 7d , substituted or unsubstituted C 6 -Cio-aryl, NR 8d R 9d , SR 10d , N0 2 or for a functional group or a heteroatom selected from among
  • R 5a , R 6a , R 7a , R 8a , R 9a , R 10a to R 5d , R 6d , R 7d , R 8d , R 9d , R 10d , R 11 , R 12 and R 13 are each independently selected from C 1 -C 6 -alkyl,
  • R 8a and R 9a , R 8b and R 9b , R 8c and R 9c , R 8d and R 9d each independently also together a cyclic Hydrocarbon radical having 2 to 8 carbon atoms, which may have one or more identical or different heteroatoms selected from the group O, S, NR 11a , and R 11a may have the meanings given for R 11 , in free and / or complexed form in which a) the aluminum-containing reaction product is subjected to a distillative separation to give an isopulegol-enriched top product and an isopulegol-depleted bottom product,
  • the bis (diarylphenol) ligands of the formula (I) obtained by the process according to the invention can usually without further purification steps in a new batch with the corresponding aluminum compounds of the formulas (II) and (III), as defined below, to the reactive catalyst complex to be implemented whereby in such recovered catalyst complexes no or no appreciable attenuation of the reactivity is observed.
  • the bis (diarylphenol) ligands of the formula (I) have two phenol systems which are each substituted in both ortho positions to the phenolic hydroxyl group by aromatics or heteroaromatics (Ar 1 to Ar 4 ) and linked together via a structural element A. and optionally further substituents (R 1 to R 4 ) can carry.
  • the aromatic or heteroaromatic substituents Ar 1 to Ar 4 may be the same or different independently of one another.
  • the two substituents each bound to a phenol system (Ar 1 and Ar 2 or Ar 3 and Ar 4 ) are the same in pairs. Most preferably, all four substituents Ar 1 to Ar 4 are the same.
  • the abovementioned substituents Ar 1 to Ar 4 are aryl radicals having 6 to 15, preferably 6 to 10 carbon atoms or heteroaryl radicals having 2 to 15, preferably 3 to 10
  • Carbon atoms are, for example, phenyl, naphthyl, anthracenyl, preferably phenyl and naphthyl.
  • the said heteroaryl radicals having 2 to 15 carbon atoms have 1 to about 6, usually 1 to 3, identical or different heteroatoms selected from the group of the heteroatoms O, S and N, on.
  • the following heteroaryl radicals may be mentioned as examples: 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4- isothiazolyl, 5-isothiazolyl,
  • aryl or heteroaryl radicals mentioned above for Ar 1 to Ar 4 can each independently be unsubstituted or carry from 1 to about 7, preferably 1 to 3, in particular 1 or 2, identical or different substituents which
  • Ci-C6-alkyl Ci-C6-perfluoroalkyl, d-Ce-alkoxy, C 7 -Ci2-aralkyl, halogen, -SiR 5a R 6a R 7a , substituted or
  • Hydrocarbon radical having from 2 to 8 carbon atoms, which may have one or more identical or different heteroatoms selected from the group O, S and NR 11a , and R 11a may have the meanings given for R 11 .
  • C 1 -C 6 -alkyl for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, pentyl, cyclopentyl, 1-methylbutyl,
  • C 1 -C 6 -perfluoroalkyl such as, for example, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl;
  • C 1 -C 6 -alkoxy such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy and 1, 1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methoxylbutoxy, 1, 1 Dimethylpropoxy, 1,2-dimethylpropoxy,
  • C 7 -C 12 aralkyl such as benzyl, 1-phenylethyl, 2-phenylethyl
  • Ci-Cio-Acyloxy such as acetyloxy, propionyloxy
  • Ci-Cio-carboxyl such as methoxycarbonyl, ethoxycarbonyl,
  • Ci-Cio-acyl such as formyl, acetyl, propionyl.
  • substituted or unsubstituted C6-Cio-aryl in the context of the present invention represents aryl radicals which, as mentioned above, have one or more, generally from 1 to about 3, identical or different substituents, where the substituents are, for example, C 6 alkyl, C 1 -C 6 perfluoroalkyl, C 1 -C 6 alkoxy, C 7 -C 12 aralkyl, halogen, silyl, dialkylamino and nitro.
  • halogen in the context of the present invention is fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine.
  • substituents -SiR 5a R 6a R 7a to -SiR 5d R 6d R 7d are in the context of
  • the silyl substituents trimethylsilyl, triethylsilyl, tert-butyl-dimethylsilyl and tert-butyl-diphenylsilyl may be mentioned as examples.
  • amino substituents which each independently carry two identical or different, preferably two identical radicals, which are selected from the above-described radicals C 1 -C 6 -alkyl, C 7 -C 12 -aralkyl and / or substituted or unsubstituted C 6 -C 10 aryl.
  • amino substituents dimethylamino, diethylamino, dibenzylamino, diallylamino, diisopropylamino.
  • radicals R.sup.8a and R.sup.9a to R.sup.8d and R.sup.9d may each together also form a cyclic hydrocarbon radical having 2 to 8 carbon atoms which has one or more identical or different heteroatoms selected from the group O, S , NR 11a .
  • the radical R 11a may be as described above C1-C6-alkyl, C7-Ci2-aralkyl and / or substituted or unsubstituted C6-Cio-aryl.
  • R 8a and R 9a to R 8d and R 9d may be mentioned as follows: piperidinyl, morpholinyl, N-methylpiperazinyl, N-benzylpiperazinyl.
  • the radical R 10a is as defined above
  • heteroaromatic substituents Ar 1 , Ar 2 , Ar 3 , Ar 4 for example phenyl,
  • the radicals Ar 1 , Ar 2 , Ar 3 , Ar 4 are identical and are preferably 4-fluorophenyl, 4-chlorophenyl, 3-chlorophenyl, 3,5-dichlorophenyl,
  • the substituents R 1 , R 2 , R 3 , R 4 corresponding to the respective phenolic hydroxyl groups can be identical or different, preferably identical, and in each case independently of one another hydrogen and / or C 1 -C 6 -alkyl as mentioned above , C 1 -C 6 -perfluoroalkyl, C 1 -C 6 -alkoxy, C 7 -C 12 -aralkyl, halogen, -SiR 5b R 6b , R 7b , substituted or unsubstituted C 6 -C 10 -aryl, -NR 8b R 9b , -SR 10b and / or -N0 2 mean.
  • radicals R 1 , R 2 , R 3 , R 4 are: methyl, ethyl, isopropyl, halogen, in particular fluorine and / or chlorine, trifluoromethyl, phenyl, methoxy, nitro.
  • the radicals R 1 , R 2 , R 3 , R 4 are the same and are particularly preferably
  • radicals R 1 or R 2 and / or R 3 or R 4 may be used together with the
  • Structure element A also form a cyclic aromatic or non-aromatic cycle. In these cases, the invention used according to
  • Bis (diarylphenol) ligands of the formula (I) a tricyclic skeleton, for example an anthracene skeleton of the formula (X) or basic skeletons of the type (XI), on:
  • the structural element A in formula (I) may be a straight-chain or branched and / or cyclic hydrocarbon radical having 1 to 25 carbon atoms, which may be saturated or mono- or polyunsaturated, usually 1 to about 6-fold unsaturated and / or partially can be aromatic.
  • the hydrocarbon radicals mentioned may optionally contain one or more, usually 1 to 3, identical or different heteroatoms selected from the group of
  • the structural element A in formula (I) preferably represents a straight-chain or branched and / or cyclic hydrocarbon radical having 1 to 25, preferably 1 to 15, and particularly preferably 1 to 10 carbon atoms, which may be saturated or mono- to tri-unsaturated and / or or partially aromatic.
  • the preferred hydrocarbon radicals may optionally have one or more, usually 1 to 3, identical or different heteroatoms selected from the group of heteroatoms O, S and NR 11 and / or one or more C (O) groups and optionally one or several same or different
  • structural elements A in formula (I) are without any
  • the illustrated structural elements 1 to 44 can each carry the substituents as described above and optionally have further, usually 1 or 2 ethylenic double bonds.
  • the structural element A can also be an aryl radical having 6 to 15, preferably 6 to 10 carbon atoms, especially a phenylene, naphthylene or Anthracenylenrest or stand for a heteroaryl radical as defined above having 2 to 15, preferably 3 to 10 carbon atoms.
  • aryl or heteroaryl radicals may optionally carry in each case 1 to 5 substituents which are selected from the group of the substituents C 1 -C 6 -alkyl, C 1 -C 6 -perfluoroalkyl, C 1 -C 6 -alkoxy, C 7 -C 12 -aralkyl described above , Halogen, -SiR 5d R 6d , R 7d , substituted or unsubstituted Ce-do-aryl, - NR 8d R 9d , SR 10d and NO 2 .
  • the structural element A can also be a functional group or a heteroatom which are selected from the group -O-, -S-, -N (R 11 ) -, -S (O) -, -C (O) -, -S (O) 2 -, -P (R 11 ) -, - (R 11 ) P (0) -, -OP (0) 0 -, -OP (0) 2 0- and -Si (R 12 ) (R 13 ) -, wherein the radicals R 11 , R 12 , R 13 are each independently as above
  • Ci-C6-alkyl, C7-Ci2-aralkyl and / or substituted or unsubstituted C6-Cio-aryl In the context of this group, the structural element A is preferably -O-, -S-, -S (O) -, -S (0) 2 - or -Si (R 12 ) (R 13 ) -.
  • ligand in free or complex-bound form encompasses both the free form of the ligand and all conceivable forms which, under the process conditions, are in the free form
  • aqueous base generally encompasses aqueous solutions whose pH value is greater than 7.
  • they are aqueous solutions of alkali metal and alkaline earth metal hydroxides, especially aqueous solutions of KOH and NaOH.
  • the expression "aluminum-containing reaction product” describes a reaction product which comprises at least one compound which contains aluminum ionically, covalently or complex-bound. These are compounds of aluminum as obtained under the conditions of the process according to the invention the compounds of the formula (R 14 ) 3-AIH P (II) or MAIH4 (III) used in the cyclization of citronellal, as defined below.
  • main amount is to be understood as meaning a percentage of the total amount of a compound present that is greater than 50%, preferably greater than 80% and particularly preferably greater than 90%.
  • step a) of the process according to the invention the aluminum-containing compound
  • a solvent which boils higher than the isopulegol is used in step a).
  • the ligands of the formula (I) contained therein are not free of solvent during the separation of the isopulegol.
  • the higher boiling solvent may be added to the aluminum containing reaction product before and / or during the distillative separation.
  • a higher boiling solvent is used whose boiling point is above the boiling point of the isopulegol under the conditions of distillation.
  • the boiling point of the solvent supplied under the conditions of distillation at least 5 ° C, preferably at least 10 ° C and in particular at least 20 ° C, above the boiling point of isopulegol.
  • Preferred higher-boiling solvents which have such a boiling point are, for example, hydrocarbons, such as phenylcyclohexane, benzyltoluene,
  • Dibenzyl ethers as well as technical mixtures of these solvents. Particular preference is given to mixtures which contain phenylcyclohexane as the main constituent.
  • an organic phase comprising the higher boiling solvent, the majority of the ligand of the formula (I) and optionally at least one aluminum-containing compound.
  • the distillative removal of isopulegol in step a) preferably takes place at a bottom temperature of preferably at most 250 ° C., preferably at most 150 ° C. and particularly preferably at most 100 ° C.
  • the bottom bottom temperature is generally not critical and is generally at least 0 ° C, preferably
  • the distillation can be carried out, if desired, under a suitable vacuum.
  • the pressure in step a) of the process according to the invention is, irrespective of the specific embodiment, generally in a range from 0.1 to 1500 mbar, preferably in a range from 1 to 500 mbar and most preferably in a range from 5 to 100 mbar.
  • Solvent the distillative separation of isopulegol continuously or discontinuously, preferably continuously.
  • the higher-boiling solvent is added to the reaction product from the cyclization of citronellal prior to the separation by distillation and added in the course of the distillation in the bottom of the amount of high-boiling
  • step a For distillative separation in step a), it is possible to use the customary devices known to the person skilled in the art (see, for example, Sattler, Thermische
  • distillation columns and columns which may be provided with packages, internals, etc.
  • the distillation columns used may contain separating internals, such as separating trays, for. As perforated plates, bubble trays or valve trays, ordered packs, z. As sheet or tissue packs, or random beds of packing.
  • the number of stages and the reflux ratio required in the column (s) used depend essentially on the purity requirements and the relative boiling position of the constituents of the aluminum-containing reaction product from the preparation of isopulegol by cyclization of citronellal and the higher-boiling solvent the concrete design and operating data can determine by known methods.
  • the distillative separation can z. B. in one or more coupled distillation columns.
  • step a) For distillative separation in step a) are also conventional evaporators, preferably evaporators with forced circulation, particularly preferably falling film evaporator.
  • composition of the overhead product obtained in the separation by distillation make it necessary to subject this optionally to a further work-up step.
  • reaction product Preparation of an aluminum-containing reaction product from the production of isopulegol by cyclization of citronellal, the reaction product additionally contains a lower boiling solvent (iii).
  • lower boiling solvent (iii) refers to the boiling point of the isopulegol, particularly those solvents or solvent mixtures which, under the conditions of distillative separation, have a boiling point which is at least 5 ° C., are preferred 10 ° C., and in particular 20 ° C., below that of the isopulegol under the respective conditions, Preferred solvents having such a boiling point are within the scope of
  • organic solvents or mixtures thereof such as aromatic solvents, for.
  • aromatic solvents for.
  • halogenated solvents eg.
  • dichloromethane, dichloroethane or chlorobenzene e.g.
  • aliphatic solvents e.g.
  • Tetrahydrofuran diethyl ether, methyl tert-butyl ether, esters, e.g. Ethyl acetate, or dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and the like.
  • esters e.g. Ethyl acetate, or dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and the like.
  • the aluminum-containing reaction product to be worked up contains such a lower-boiling solvent, then, in a suitable embodiment, this is at least partially removed from the distillative separation of the isopulegol
  • the separation of the lower-boiling solvent is preferably also carried out by distillation. Depending on the boiling point of the lower boiling solvent, the usual previously mentioned
  • Distillation devices are used.
  • the distillative separation of the aluminum-containing reaction product in step a) is carried out to obtain an isopulegol-enriched overhead product which simultaneously contains at least a portion, preferably the major amount of the lower-boiling solvent.
  • the top product can be subjected to a further separation, preferably also by distillation.
  • the separated lower-boiling solvent is advantageously recycled to the cyclization of the citronellal, in which it is used as a solvent.
  • the process of the invention requires - except for additions, which are required by inevitable losses - the only one-time provision of a quantity of lower-boiling solvent.
  • the reaction product additionally contains an adjuvant (iv).
  • adjuvant (iv) in the context of the present invention refers to compounds which are added in the cyclization of citronellal in order to suppress unwanted side reactions, preference being given to the adjuvants (iv) selected from organic acids, carboxylic anhydrides, aldehydes, ketones and vinyl ethers.
  • the excipients (iv) are selected from acids, preferably organic acids.
  • the auxiliaries (iv) are selected from carboxylic acid anhydrides, aldehydes, ketones and vinyl ethers.
  • auxiliaries (iv) of the mentioned substance classes can each be present individually or in the form of mixtures in the reaction product to be worked up.
  • Preferred mixtures are those which consist of compounds of a substance class.
  • the reaction product contains a single adjuvant.
  • the auxiliaries (iv) contained in the reaction product from the cyclization of citronellal are also at least partially removed and recycled as far as possible into the cyclization of citronellal. If the auxiliaries (iv) have, under the conditions of the distillation, a boiling point which is below or only slightly above 30 ° C. above the boiling point of the isopulegol, they can largely and to the extent possible, by distillation, from the reacted mixture which it was not implemented, if necessary. Depending on the boiling point of the excipient, the usual distillation devices mentioned above can be used.
  • Isopulegols lies, they remain in the bottom product and are optionally removed in step b) of the method according to the invention, if your physical properties allow this.
  • the distillative separation of the reaction product in step a) is carried out to obtain an isopulegol-enriched overhead product which simultaneously contains at least a portion, preferably the major amount of the adjuvant (iv).
  • this major product may contain a lower boiling solvent, as previously stated.
  • the top product can be subjected to a further separation, preferably also by distillation.
  • the separated excipient (iv), optionally together with the lower-boiling solvent, is advantageously attributed to the cyclization of the citronellal, in which it can, for. B. is used to suppress unwanted side reactions.
  • the process of the invention requires - except for supplements, which are required by inevitable losses - the only one-time provision of an amount of the excipient (iv).
  • the isopulegol separation, the feed of the higher boiling solvent and optionally the low boiler removal, d. H. the separation of optional solvents and volatile excipients from the cyclization of citronellal can be combined in different ways:
  • a so-called dividing wall column is used for the distillation, d.
  • Feed point and a side draw are located on opposite sides of a partition, extending over a section of the
  • distillation columns which contain a partition wall are known per se to the person skilled in the art. Provided side draw and inlet are located in the area of the partition, creates a circuit analogous to a Brugma or Petlyuk circuit.
  • Such distillations using dividing wall columns are described in DE-A-33 02 525 and EP-A-0 804 951, to which reference is made in its entirety.
  • z. B. as the top product enriched fraction of light ends and withdrawn as a side draw a main part of isopulegol containing stream.
  • reaction product of the cyclization of citronellal contains a solvent and / or a volatile excipient, as described in more detail below.
  • mixtures of isopulegol and lower or slightly higher boiling solvents and / or adjuvant (iv) can form the top product of the first column and in the second column of a separation to obtain a stream containing at least the majority of the isopulegol and a
  • Streams containing lower-boiling solvent (iii) and auxiliary (iv) of the cyclization can be recycled to the cyclization usually without further separation.
  • the ligands of the formula (I) are obtained, optionally in the form of their complexes or other derivatives, as the bottom product of the first column.
  • step b) of the process according to the invention the isopulegol-depleted bottom product is brought into intimate contact with an aqueous base to give an aluminum-containing aqueous phase and an organic phase containing the majority of the ligands of the formula (I).
  • aqueous bases are those mentioned above.
  • the isopulegol depleted bottom product obtained in step a) can, in addition to the ligand of the formula (I) in free or complex-bound form, at least one contain further low volatility component.
  • these include z. B. in step a) added higher boiling solvents, the reaction products of the
  • step a) Compounds and optionally in step a) not separated excipients (iv). Since aluminum-containing components and / or the auxiliaries (iv) accumulate in particular in a continuous process and have a negative effect on the yield and purity of the separation in step c), it is advantageous to remove these compounds as completely as possible. This applies especially to the aluminum-containing compounds.
  • the contacting in step b) is preferably carried out by extraction.
  • the number of extraction stages is preferably in a range of 1 to 20 stages.
  • extractants used are the abovementioned aqueous bases. Therefore, these terms are used synonymously in the context of the present invention.
  • the isopulegol-depleted bottom product from step a) is intimately contacted with an aqueous base. After separation of the phases to obtain a main amount of the ligand of the formula (I) containing phase and an
  • Aluminum-containing compounds enriched aqueous phase is removed.
  • the contacting can be continuous or discontinuous.
  • discontinuous implementation brings under mechanical movement, for. B. by stirring, the isopulegol depleted bottom product from step a) and the aqueous extractant in a suitable vessel in contact, the mixture is allowed to rest for phase separation and removes one of the phases by
  • Main amount of the ligand of the formula (I) containing phase in each case with a fresh portion of the aqueous extractant is brought into contact and / or the aqueous extractant is passed in countercurrent.
  • the extraction is carried out continuously.
  • the aqueous extractant and the stream of it are introduced
  • Isopulegol depleted bottom product from step a) suitable apparatus in an analogous manner to the discontinuous variant continuously.
  • the apparatus in which the separation of the phases takes place a discharge of the main amount
  • the extraction is carried out at least one stage, z. B. in a mixer-separator combination.
  • Suitable mixers are both dynamic and static mixers. Extraction in several stages takes place, for example, in several mixer separators or extraction columns.
  • At least one coalescing device is used to improve the phase separation. This is preferably selected from coalescing filters, electrocoalescers and combinations thereof. When using mixer-settler extraction equipment, the use of
  • Coalescing filters such as candle or sand filters, have been found to be advantageous for improving the phase separation.
  • the filter can be installed directly after the mixer (agitator) and / or in the organic drain of the separator. Further preferred for improving the phase separation is the use of
  • Electrocoalescers These have proved to be effective in the separation of aqueous foreign phases of up to 5% by mass.
  • the use of coalescing apparatuses in the process according to the invention is also advantageously suitable for the separation of finely dispersed aqueous phase from the organic discharge of an extraction column containing the major amount of the ligand of the formula (I).
  • the extraction is carried out in at least one mixer-separator combination for the extraction of aluminum-containing components from the isopulegol-depleted bottom product from step a).
  • a further mixer-precipitator combination is particularly advantageous in order subsequently to re-extract fractions of the ligand of the formula (I) or, if appropriate, of the higher-boiling solvent, which may optionally undergo partial transition into the extractant with the aluminum-containing compounds to be separated off, and thus due to the procedure.
  • the extraction is carried out continuously in two successive, heatable mixers, wherein the aqueous base is introduced with the isopulegol depleted bottom product from step a) in the first stirring apparatus and the resulting mixture is transferred to a second stirring apparatus. From this second stirring apparatus, the mixture is then introduced into a separator in which the phase separation takes place in a heavier aqueous and a lighter organic phase. By this cascading the mixer becomes a more complete
  • Agitators come to those skilled in the art equipped with stirrers and with steam or hot water heated container (stirred tank) for use.
  • a phase separation vessel a horizontally installed, also heatable container is advantageously used, which is heated so that no solids can be separated from the individual phases.
  • Suitable drying processes are the usual, known in the art, in particular the adsorption on dehydrating agents, eg. Using a zeolitic molecular sieve.
  • the water is removed completely or at least partially by distillation.
  • the concentration of the ligand in the organic phase exceed its solubility. This can be done by a suitable choice of the temperature and / or the amount and type of optionally added solvent.
  • a discharge of the heated bottom product from step a) is brought into intimate contact with a heated aqueous base.
  • heated in the context of the present invention denotes a temperature above room temperature and below the respective
  • Boiling point temperatures of the aqueous or organic solutions under the respective reaction conditions means a temperature in the range of 25 ° C to 150 ° C, especially in the range of 70 ° C to 100 ° C.
  • the isopulegol-depleted bottom product may optionally contain further components not separated off in step a). These are preferably separated in step b).
  • the resulting aqueous phase may be subjected to a suitable separation process to remove these components, e.g. B.
  • electromagnetic radiation is radiated into the solution and the intensity of the electromagnetic radiation scattered by the crystals in the solution is detected. In this case, they are crystals of the ligand.
  • the detected intensity is then compared with the desired intensity and the temperature of the solution is controlled in dependence on the difference of the detected intensity and the target intensity so that this difference is reduced. Finally, when the amount of the difference of the detected intensity and the target intensity is smaller than the threshold, the
  • Crystallization process in particular the cooling crystallization started.
  • the recovered crystals of the ligand are then separated.
  • the benchmark for this is the achievement of a filter resistance which is 5 * 10 13 mPasnr 2 for a product which filters well. If the solution is inoculated too strongly or too low, the filter resistance changes by more than an order of magnitude to more than 10 15 mPasnr 2 .
  • the solution or part of the solution in a crystallization vessel is preferably brought to a temperature which is lower than 95 ° C, especially lower than 90 ° C.
  • the temperature is then increased until the detected intensity of the scattered electromagnetic radiation as described has approached the target intensity. Thereafter, the temperature for the cooling crystallization is lowered again.
  • the cooling rate is initially in a range of 1 K / h to 5 K / h.
  • Seed amount provided at the beginning of the crystallization process This ensures that despite the complex molecular structure of the ligand, this can be recovered in a short time in high yield. In this crystallization process, it may in addition to the described
  • Evaporation crystallization process a vacuum crystallization process, and a process employing crystallizers or spray crystallizers.
  • the crystallization is carried out at a temperature in the range of -50 ° C to 150 ° C, preferably in the range of 0 ° C to 120 ° C and especially in a range of 30 ° C to 1 10 ° C.
  • the crystalline ligand of the formula (I) can be isolated from the solution, for example by filtration, flotation, centrifugation or sieving.
  • the ligand of the formula (I) thus obtained can optionally be dried by suitable drying processes.
  • suitable drying processes Methods for this are known in the art.
  • the organic phase depleted in ligand of formula (I) can be recycled to the process before or during step a).
  • the ligand of the formula (I) is selected from bis (diarylphenol) ligands of the formula (I.a)
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , R 1 , R 2 , R 3 , R 4 and A have the meanings given above.
  • the ligands of formula (I.a) also have two phenolic systems, each in both ortho positions to the phenolic hydroxy group by aromatics or
  • Heteroaromaten (Ar 1 to Ar 4 ) are substituted and are linked together via a structural element A and optionally may carry further substituents (R 1 to R 4 ), wherein the structural element A in each case in the para position to the phenolic hydroxy group with the two Phenolic systems is linked.
  • the radicals Ar 1 , Ar 2 , Ar 3 , Ar 4 , the radicals R 1 , R 2 , R 3 , R 4 and the structural element A can have the same meanings as mentioned above for formula (I).
  • Particularly preferred ligands according to the invention are those in which the aryl radicals Ar 1 , Ar 2 , Ar 3 and Ar 4 are the same and which have been described above for formula (I)
  • Aryl radicals Ar 1 to Ar 4 are phenyl, naphthyl, 4-fluorophenyl, 4-chlorophenyl, 3-chlorophenyl, 3,5-dichlorophenyl, 4-methylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, very particularly preferably phenyl.
  • the radicals R 1 , R 2 , R 3 and R 4 are identical or different, preferably identical, and are preferably hydrogen, halogen, in particular fluorine or chlorine, methyl, trifluoromethyl, isopropyl, tert-butyl, phenyl, nitro.
  • Structural element A in formula (Ia) has the meanings given above for formula (I).
  • Preferred structural elements A in formula (Ia) are in particular also the structural elements 1 to 44, which may be substituted in the manner mentioned.
  • Particularly preferred ligands are those of the formulas (Ia) to (Ia3), where the abovementioned radicals Ar 1 to Ar 4 , R 1 to R 4 and R 15 to R 18 preferably have the meanings given in the table as examples:
  • Ph stands for a phenyl radical and C (O) in the context of the present invention represents a carbonyl group.
  • the radicals R 15 , R 16 and R 17 independently of one another may be C 1 -C 6 -alkyl as defined above, C 1 -C 10 -acyl, C 1 -C 10 -carboxyl or C 6 -C 10 -aryl, where the radicals mentioned are one or more the same or different halogen and / or NO 2 substituents can carry and wherein the radicals R 16 and R 17 together can also form a cyclic structural element, preferably an alkylene bridge.
  • the substance is a ligand of the formula (I) selected from bis (diarylphenol) ligands of the above formula (Ia).
  • Particularly preferred ligands are those of the above formulas (Ia) to (Ia 3 ), wherein the aforementioned radicals Ar 1 to Ar 4 , R 1 to R 4 and R 15 to R 18 preferably have the meanings given above in table form.
  • Another object of the present invention relates to a process for the preparation of isopulegol of the forms
  • R 14 is a branched or unbranched alkyl radical having 1 to 5
  • p is 0 or an integer from 1 to 3, and / or with an aluminum compound of the formula
  • M means lithium, sodium or potassium
  • the separation of the ligand of formula (I) takes place by crystallization, in the context of the method described above for separating a substance from a solution.
  • the bis (diarylphenol) ligands of the formulas (I) or (I.a) which can be used to prepare the bis (diarylphenoxy) -aluminum compounds used according to the invention can easily be prepared by methods known per se to the person skilled in the art.
  • Compounds of the structural type (la-1) are obtained, for example, by reacting the corresponding bis-ortho-arylphenols with an aldehyde R 15 CHO in the presence of a Lewis acid, for example AlC, as described, inter alia, by ZY Wang, AS Hay in Synthesis 1989, 471 -472 or in US 3,739,035.
  • Ligands of the structure type (la 2 ) are accessible, for example, by reacting the corresponding bis-ortho-arylphenols with a suitable ketone of the formula R 16 C (O) R 17 , as described, for example, in US Pat. No. 3,739,035.
  • Ligands of the structural type (I.a3) are, for example, accessible by Friedel-Crafts acylation of the corresponding phenols or
  • the bis (diarylphenoxy) aluminum compounds used according to the invention are obtained, for example, by reacting the above-described bis (diarylphenol) ligands of the formulas (I) or (Ia) with an aluminum compound of the formula (II)
  • R 14 is a branched or unbranched alkyl radical having 1 to 5 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl or neopentyl.
  • the index p is 0 or an integer from 1 to 3.
  • the index p is preferably 1 or 0, particularly preferably 0.
  • Preferred compounds of the formula (II) are, for example, trimethylaluminum,
  • Trimethylaluminum and triethylaluminum Trimethylaluminum and triethylaluminum.
  • the bis (diarylphenoxy) aluminum compounds used according to the invention are also obtained by reacting the bis (diarylphenol) ligands of the formulas (I) or (I.a) described above with an aluminum compound of the formula (III)
  • MAIH 4 where M is lithium, sodium or potassium. Accordingly, are suitable for
  • Bis (diarylphenol) ligands of the formulas (I) or (I.a) are suitable.
  • reaction is advantageously carried out such that one of the bis (diarylphenol) ligands of the formulas (I) or (I.a) described above with a
  • reaction is carried out in an inert organic solvent such as toluene, cyclohexane, dichloromethane, xylene, ethylbenzene, chlorobenzene, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, ethyl acetate, pentane, hexane,
  • an inert organic solvent such as toluene, cyclohexane, dichloromethane, xylene, ethylbenzene, chlorobenzene, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, ethyl acetate, pentane, hexane,
  • each aluminum atom can govern with 1 to 3 phenolic hydroxy groups. Due to the steric properties or requirements of the bis (diarylphenol) ligands of the formulas (I) or (I.a) used, higher molecular structures such as linear structures or networks can be formed.
  • the molar ratio of the bis (diarylphenol) ligands of the formulas (I) or (Ia) used to the compounds of the formula (II) and / or (III) used is chosen such that the amount of unreacted compounds of the formula (II) Formulas (II) and / or (III) is as low as possible.
  • the said ratio is chosen such that after contacting the bis (diarylphenol) ligands of the formulas (I) or (Ia) with the compound or compounds (II) and (III) no unreacted compound of the formula (II) and / or (III).
  • a suitable organic solvent for example toluene
  • reaction between the ligands of the formula (I) or (Ia) used and the aluminum compounds of the formulas (II) and / or (III) is generally rapid and is usually, depending on the chosen reaction conditions, after about 10 min until about 2 h, often after about 1 h, completed.
  • reaction-carrier Reactants may be advantageous to increase the temperature of the reaction mixture for a short time.
  • Bis (diarylphenoxy) aluminum compounds can be further used in the respectively obtained form or separated off and freed from the solvents used.
  • the isolation can be known and advantageous according to those skilled in the art
  • the isolation, storage or further treatment of the bis (diarylphenoxy) aluminum compounds used in accordance with the invention is preferably carried out with substantial exclusion of oxygen and moisture.
  • citronellal can be added as such or in the form of a solution, advantageously in one of the abovementioned suitable solvents.
  • a solution of the selected ligand of the formulas (I) or (Ia) in toluene is first prepared and then, advantageously with stirring, the selected aluminum compound of the formula (II) and / or ( III), preferably trimethyl or triethylaluminum in toluene, solution to.
  • citronellal As a starting material for carrying out the cyclization process according to the invention is citronellal, which may be prepared by any method. Citronellal is preferably used which has a purity of from about 90 to about 99.9% by weight, more preferably from about 95 to about 99.9% by weight.
  • citronellal to be cyclized is advantageously carried out at temperatures in the range of about -40 ° C to about 40 ° C, preferably in the range of about -20 ° C to about 20 ° C.
  • the prepared solution of the invention is advantageous
  • the addition of the citronellal or the solution thereof may be carried out by either adding the entire amount at once or adding it in portions or continuously to the prepared catalyst solution.
  • Suitable solvents are in turn the abovementioned solvents, in particular toluene. Preference is given to the citronellal to be cyclized as such, d. H. without further addition of solvents. When using a solvent, the entire solvent of the citronellal or the solution thereof may be carried out by either adding the entire amount at once or adding it in portions or continuously to the prepared catalyst solution.
  • Suitable solvents are in turn the abovementioned solvents, in particular toluene. Preference is given to the citronellal to be cyclized as such, d. H. without further addition of solvents. When using a solvent, the entire
  • Cyclization reaction advantageously chosen so that the volume-related ratio of citronellal to be converted to the solvent about 2: 1 to about 1: 20, preferably from about 1, 5: 1 to about 1: 10.
  • the amount ratio between the citronellal to be reacted and the amount of the bis (diarylphenoxy) aluminum compound used according to the invention is determined by the amount of the compounds of the formula (I) or (La) and of the formula (II) and / or (III), that is determined by the amount ratio of ligand used to aluminum compound of formula (II) and / or (III).
  • the amount of citronellal to be converted to the amount of aluminum compound of the formula (II) and / or (III) used is chosen such that the molar ratio is about 5: 1 to about 1000: 1, preferably about 10: 1 to about 500 : 1, more preferably about 50: 1 to about 200: 1.
  • the ratio between the ligand of the formula (I) or (Ia) used and the aluminum compound of the formula (II) and / or (III) used in the bis (diarylphenoxy) -aluminum compound described above can be used be varied.
  • citronalal to isopulegol occurs depending on the choice of
  • Reaction partner and reaction conditions usually fast and is usually after about 0.5 to about 10 h, often after about 5 h, largely completed.
  • the progress of the reaction can be easily followed by methods known per se to the person skilled in the art, for example by chromatographic, especially gas chromatographic methods or else HPLC methods.
  • an adjuvant for example an acid, preferably an organic acid.
  • organic acids examples which may be mentioned as advantageously usable organic acids: acetic acid, propionic acid, benzoic acid, toluenesulfonic acid, methanesulfonic acid, are preferred
  • Acetic acid is advantageously used in an amount of from about 0.5 to about 10% by weight, based on the amount of citronellal to be converted. They will be advantageous together with the Citronellal, z. B. in the form of a mixture added to the reaction mixture.
  • the process according to the invention for the preparation of isopulegol is carried out by cyclization of citronellal
  • Carboxylic acid anhydrides aldehydes, ketones and vinyl ethers.
  • the adjuvants (iv) of the substance classes mentioned can each be used individually or in the form of mixtures with one another. In the case of mixtures, preference is given to using those which consist of compounds of a substance class.
  • the cyclization of citronellal is carried out in the presence of a carboxylic acid anhydride of the formula (VI) where the radicals R 20 and R 20 'may be identical or different, preferably identical, and a branched or unbranched C 1 -C 12 -alkyl radical or
  • C7-C12-aralkyl radical or a C6-Cio-aryl radical where the radicals mentioned each have one or more, usually 1 to about 3, identical or different substituents selected from the group OR 10e , SR 10f NR 8e R 9e and Halogen and wherein R 20 and R 20 ' together may also form a 5- to 8-membered ring having one or more ethylenic double bonds and one or more identical or different heteroatoms selected from the group O, S and NR 11b and R 10e , R 10f , R 8e , R 9e and R 11b may have the meanings given above for R 11 .
  • the cyclization of citronellal is carried out in the presence of an aldehyde of the formula (VII) in which the radical R 21 is a branched or unbranched C 1 -C 12 -alkyl radical or C 7 -C 12 -aralkyl radical or a C 6 -C 10 -aryl radical, where the radicals mentioned are each one or more, preferably 1 to 3, identical or different
  • Substituents selected from the group OR 10e , SR 10f may have NR 8e R 9e and halogen, wherein R 10e , R 10f , R 8e and R 9e may have the meanings given above for R 11 .
  • cyclization of citronellal is carried out in the presence of a ketone of the formula (VIII) in which the radicals R 22 and R 23 may each be identical or different and denote a branched or unbranched C 1 -C 12 -alkyl radical or C 7 -C 12 -aralkyl radical or a C 6 -C 10 -aryl radical or a C 1 -C 6 -alkoxycarbonyl radical, where each of said radicals may have one or more, preferably 1 to 3, identical or different substituents selected from the group OR 10e , SR 10f NR 8e R 9e and halogen, and where R 22 and R 23 together also have a 5- to 8- may form a membered ring having one or more ethylenic double bonds and one or more identical or different heteroatoms selected from the group consisting of O, S, NR 11b and wherein R 10e , R 10f , R 8e , R 9e and R
  • radicals R 24 , R 25 , R 26 and R 27 independently of one another may be the same or different and a branched or unbranched C 1 -C 12 -alkyl radical or C 7 -C 12 -aralkyl radical or a C 6 -C 10 -aryl radical, where the radicals mentioned each have one or more, preferably 1 to 3, identical or different substituents selected from oxo, OR 10e , SR 10f NR 8e R 9e and halogen and wherein R 25 and R 26 may together also form a 5- to 8-membered ring having one or more ethylenic double bonds and one or more, usually 1 or 2, identical or different heteroatoms R 10e , R 10f , R 8e , R 9e and R 11b may have the meanings given above for R 11 , selected from the group O, S, NR 11b .
  • Ci-Ci2-Alkyl stands for as described above Ci-C6-alkyl and beyond, for example, heptyl, octyl, nonyl, decyl, undecyl or dodecyl. In the cases where two alkyl radicals together form a ring are under
  • Alkyl radicals also alkylenyl to understand. C7-C12 aralkyl radicals and
  • Ci-C6-alkoxycarbonyl methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl and isopropoxycarbonyl, preferably methoxycarbonyl and ethoxycarbonyl.
  • Ci-Ci2-alkyl radical or a C6-Cio-aryl radical are as
  • carboxylic anhydrides acetic anhydride, propionic anhydride, pivalic anhydride and benzoic anhydride.
  • aldehydes of the formula (VII) which can likewise preferably be used according to the invention include acetaldehyde, propionaldehyde and chloral (trichloroacetaldehyde). If the cyclization of citronellal is carried out in the context of a further preferred embodiment in the presence of a ketone of the formula (VIII), it is advantageous to use those having an activated, ie electron-poor, carbonyl function.
  • ketones which are particularly suitable for use in the process according to the invention: 1,1,1-trifluoroacetone, 1,1,1-trifluoroacetophenone, hexafluoroacetone, methyl pyruvic acid and pyruvic acid ethyl ester.
  • vinyl ethers of the formula (IX) may be mentioned by way of example: methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether and
  • the amount of carboxylic acid anhydride, aldehyde, ketone and / or vinyl ether to be used according to the invention can be varied within wide limits and depends on the nature of the substance used and the degree of purity or the presence of impurities not yet further identified.
  • the compounds mentioned or mixtures thereof are usually used in an amount of from about 0.01 mol% to about 5 mol%, preferably from about 0.1 mol% to about 2 mol%, based on the amount used Citronellal, a.
  • the procedure is advantageously such that initially a solution of the bis (diarylphenoxy) aluminum compound to be used according to the invention is prepared in a suitable solvent as described above. This solution is then used according to the invention preferably a mixture of the to be cyclized
  • the solution of bis (diarylphenoxy) -aluminum compound to be used according to the invention first with the optionally selected carboxylic anhydride, the aldehyde, the ketone and / or the vinyl ether and then add the citronellal to be cyclized.
  • the citronellal or the mixture of citronellal with the selected compound within a period of about 30 minutes to about 6 hours, preferably within about 2 hours to about 4 hours, to the catalyst solution or the
  • the citronellal can be added as such or in the form of a solution, advantageously in one of the abovementioned suitable solvents.
  • a solution of the selected ligand of the formulas (I) or (Ia) in toluene is first prepared and then, expediently with stirring, the selected aluminum compound of the formula (II) and / or (III), preferably trimethyl or triethylaluminum in toluene solution.
  • citronellal or the mixture of citronellal to be cyclized with the selected carboxylic acid anhydride, aldehyde, activated ketone and / or the vinyl ether takes place in the context of this embodiment advantageously at temperatures in the range from about -40 ° C to about 40 ° C, preferably in Range from about -20 ° C to about 20 ° C.
  • the prepared solution or suspension is advantageous
  • Bis (diarylphenoxy) aluminum compound of the invention to a temperature in this range, for. B. to a temperature in the range of -10 ° C to 10 ° C, cooled and added the further reactants in pre-cooled form.
  • the addition of the mixture of citronellal and the further compound chosen may be carried out by either adding all or part of the citronellal at once
  • Catalyst solution gives.
  • Suitable solvents are in turn preferably the abovementioned solvents, in particular toluene.
  • the total amount of solvent is advantageously chosen such that the volume-related ratio of citronellal to be converted to the solvent is about 1: 1 to about 1:20, preferably from about 1: 1 to about 1:10.
  • Catalyst complex is deactivated. This is inter alia ligand exchange processes between the particular bis (diarylphenol) ligands of the formula of the bis (diarylphenoxy) -aluminum compounds used and by Cyclization resulting isopulegol due.
  • the deactivated form of the catalyst is, depending on the choice of the solvents used, usually in contrast to the active polymeric catalyst in the
  • Reaction mixture are separated.
  • the retained, still active part of the catalyst can be supplemented with fresh catalyst and reused without significant loss of activity, preferably in the context of a further cyclization reaction according to the invention from citronellal to isopulegol.
  • the amount of catalyst used can be chosen so that the entire catalyst complex used in the course or after completion of the cyclization reaction of the invention is deactivated and thus soluble, which can be seen in a clear reaction mixture. It is advantageously noticeable that in this case, due to the above
  • the process according to the invention serves for the preparation of optically active isopulegol of the formula (IV.a) by cyclization of active citronellal of formula (Va) where ( * ) denotes an asymmetric carbon atom.
  • racemic or non-racemic isopulegol is a valuable intermediate for the preparation of racemic or non-racemic menthol, one of the world's most important fragrances or flavorings.
  • Menthol can be prepared by the skilled person known methods of hydrogenation, especially the catalytic hydrogenation on suitable transition metal catalysts such as in Pickard et al., J. Chem. Soc. 1920, 1253; Ohloff et al., Chem. Ber. 1962, 95, 1400; Pavia et al., Bull. Soc. Chim. 1981, 24, Otsuka et al., Synthesis 1991, 665 or in EP 1 053 974 A, can be obtained from isopulegol. With a suitable choice of the reaction conditions, the relative or absolute configuration of the isopulegol used remains largely, in many cases completely preserved.
  • Another object of the present invention therefore relates to a process for the preparation of menthol, comprising the steps:
  • this process is used to prepare optically active menthol, especially for the preparation of L - (-) - menthol from optically active L (-) isopulegol.
  • optically active menthol especially for the preparation of L - (-) - menthol from optically active L (-) isopulegol.
  • Figure 1 shows the structure of a first embodiment of
  • FIG. 2 shows the structure of the scattered light probe, which is shown in FIG.
  • FIG. 3 shows a diagram in which an example of the temperature profile and the detected intensity for an embodiment of the invention
  • FIG. 4 shows a diagram which shows the relationship between the
  • FIG. 5 shows a further exemplary embodiment of the invention
  • the device comprises a crystallization vessel 1 which has a feed line 2 and a discharge line 3. Via the feed line 2, the solution is introduced into the crystallization vessel 1. So that the introduced solution initially remains in the crystallization vessel 1, an electronically controllable valve 4 is provided in the discharge line 3, which is initially closed. After the crystallization process has been carried out in the crystallization vessel 1, the suspension with the crystals is led out of the crystallization vessel 1 through the discharge line 3.
  • a tempering 5 is provided in the supply line 2 or alternatively in a storage vessel.
  • this tempering device 5 the temperature of the solution, which is introduced via the feed line 2 into the crystallization vessel 1, can be regulated.
  • a temperature sensor 6 in the supply line 2 is provided for the temperature control.
  • a tempering device 7 and a temperature sensor 8 are provided in the crystallization vessel 1, by means of which the Temperature of the solution, which is located in the crystallization vessel 1, is measured and regulated.
  • a scattered light probe 9 which will be explained in detail later.
  • the valve 4, the tempering devices 5 and 7, the temperature sensors 6 and 8 and the scattered light probe 9 are data technically coupled to a control unit 10. In this way, the measured values of the temperature sensors 6 and 8 and the measured values of the scattered light probe 9 are applied to the
  • Control unit 10 transmitted. Furthermore, the control unit 10 controls the
  • valve 4 can be opened and closed by means of the control unit 10.
  • the separation unit 1 1 may be formed as a known filter device.
  • the scattered light probe 9 comprises a tube 12 in which the waveguides L1 and L3 are located. At the end of the tube 12, which dips into the crystallization vessel 1, the waveguide L1 has a decoupling surface and the waveguide L3 has a coupling surface.
  • the scattered light probe 9 is a radiation source 14 and an emitter for
  • the electromagnetic radiation emitted by the radiation source 14 is coupled via a coupling surface into the waveguide L1, via which the electromagnetic radiation is conducted to the outcoupling surface of the waveguide L1.
  • Electromagnetic radiation is thus as radiation S1 in the in the
  • Crystallization vessel 1 located solution irradiated.
  • the beam generated by the radiation S1 has on entry into the solution or
  • Suspension has a cross-section greater than 0.39 mm. Furthermore, the beam is divergent at an angle of about +/- 12 °, i. the opening angle of the beam is 24 °.
  • the waveguides L1 and L3 are parallel and liquid-tight through the opening 13 of the scattered light probe 9 performed. In particular, they are oriented such that the direction of the radiation S1 irradiated into the solution or suspension is parallel to the direction of detection for the radiation S2 which is scattered on the crystals and which is coupled into the waveguide L3.
  • Scatter probe 9 is immersed in the crystallization vessel 1, that in a clear solution in which there are no crystals in the solution, no radiation enters the waveguide L3, which has a wavelength in which the radiation source 14 emits radiation when over the Waveguide L1 radiation is irradiated in the clear solution.
  • the beam of the incoming radiation S2, which enters the waveguide L3, is divergent with the same aperture angle, so that the transmission and reception range of the scattered light probe 9 is spatially overlapping. This results in two adjacent cones that intersect in space. This results in a very large measurement volume, which is particularly important at very low particle concentrations.
  • the scattered light probe 9 has no disc as a conclusion between the
  • the optical offset of the scattered light probe 9 therefore approaches zero.
  • the radiation source 14 generates infrared radiation in a wavelength range of 800 nm to 900 nm.
  • the electromagnetic radiation radiated into the solution is scattered on the surfaces of crystals which are in the solution.
  • a portion of the backscattered on the crystals electromagnetic radiation S2 is guided via the coupling surface of the waveguide L3 from this to a detector 15.
  • the detector 15 is designed to measure the intensity of the electromagnetic radiation in the
  • Wavelength range can measure, in which the radiation source 14th
  • the detector 15 has a receiving electronics, which is a very wide
  • the receiving electronics deliver a voltage of 1 V at an incident light power of 20 picoW, ie at a light power of about 150 ⁇ / ⁇ 2 .
  • the detector 15 is extremely sensitive.
  • a branch is further provided in the waveguide L1.
  • a portion of the radiation generated by the radiation source 14 and coupled into the waveguide L 1 is branched off into a waveguide L 2 and fed to the detector 15.
  • the branched off via the waveguide L2 and the detector 15 supplied radiation serves as reference radiation.
  • a voltage value is generated which is directly related to the light intensity backscattered by the crystals in the solution.
  • the reference voltage value generated by the detector 15, which is caused by the reference radiation, takes into account the intensity of the radiation S1 radiated into the solution.
  • the voltage value of the detector 15 is under
  • Measuring device can be used, as described in EP 0 472 899 A1.
  • the scattered light probe described in this document can be used both for a
  • the scattered light probe 9 comprises a rod probe, which is immersed in the crystallization vessel 1.
  • the detector 15 is then connected to the rod probe via waveguides and arranged outside of the crystallization vessel l.
  • the measurement can also be carried out with a detector 15 without referencing the radiation source 14.
  • the referencing with a second detector is advantageous.
  • the correction of the scatter signal, which is detected by the detector 15, then takes place on the basis of the reference signal, which is detected by a further detector in an evaluation unit, which then generates a corrected leakage signal and transmits it to the control unit 10.
  • both one and several waveguides can serve as transmitters and receivers.
  • the fiber geometry does not necessarily have to be realized with parallel transmitting and receiving fibers, although this is preferred.
  • a solution with disc in front of the fiber ends with deviating could be
  • the scattered light probe 9 does not detect the complete scattered radiation. Due to multiple scattering, transmission and absorption and due to the spatially limited receiving cone (aperture), the scattered light probe 9 detects only a proportional to the particle surface portion of the scattered radiation.
  • the ligand la2-3 described in the introduction which is dissolved in phenylcyclohexane, is to be separated off.
  • the solution was prepared as the bottom product from the cyclization of citronellal in the presence of a
  • the solution is introduced into the crystallization vessel 1 at a temperature which is a few 10 K below the expected saturation temperature.
  • the solution is supplied at a temperature of 80 ° C. This temperature is determined by means of the control unit 10, the temperature control devices 5 and 7 and the
  • Temperature sensors 6 and 8 set. At this temperature is a very large amount of crystals of the ligand in the solution. However, the crystal size and morphology of the crystals is unsuitable for later filtration in the separation unit 11. Now, the temperature of the solution, which is introduced into the crystallization vessel 1, raised by means of the tempering device 5. At the same time by means of
  • Stray light probe 9 irradiated electromagnetic radiation into the solution. From the control unit 10, the temperature of the solution is then detected continuously by means of the temperature sensor 8. Further, the intensity of the backscattered
  • Cooling crystallization process started in which the solution is cooled again with a certain cooling curve, so that crystals of the ligand form. The crystals are then filtered out in the separation unit 11, and the size and morphology of these crystals are examined.
  • the reference measurements are now carried out for a variety of intensities, in which the subsequent crystallization process is carried out in always the same way.
  • the reference measurement is then determined at which the ideal crystal size and morphology for the separation has been generated.
  • Crystallization method of this reference measurement d. H. the minimum intensity of the backscattered electromagnetic radiation in this reference measurement is defined as the desired intensity ls. At this desired intensity ls is the size of the
  • Crystal surface which is formed by the seed crystals of the ligand, ideal for the subsequent crystallization process.
  • an initial temperature value TA is set in advance, at which the solution is introduced into the crystallization vessel 1 at the beginning of the process.
  • Initial temperature value TA is significantly below the temperature value ⁇ , which corresponds to the desired intensity ls, d. H. the outlet temperature for the
  • the initial temperature value TA is about 90 ° C.
  • this initial temperature value TA can also be determined from the desired intensity ls by selecting the initial intensity associated with the initial temperature value TA for the backscattered electromagnetic radiation as the x-fold intensity of the desired intensity ls.
  • the value x can be in a range of 1, 2 to 1 0. In the present case, the value x is 6.5.
  • the process for separating the ligand from the solution supplied via the feed line 2 is then carried out as follows after the determination of the desired intensity and of the initial temperature value:
  • the solution is supplied via the supply line 2 with the initial temperature value TA.
  • the intensity I of the electromagnetic radiation backscattered on the crystals is detected by the control unit 10.
  • FIG. 3 shows the time profile of the signal I of the scattered light probe 9, which correlates with the intensity I of the backscattered electromagnetic radiation, as well as the associated time profile of the temperature T of the solution.
  • Initial temperature value TA in this case is 89.1 3 ° C.
  • the associated signal of the scattered light probe 9 is 0.85 V.
  • the signal I of the scattered light probe 9 and the intensity I of the backscattered electromagnetic radiation, since these are directly related.
  • the control unit 10 By means of the control unit 10, the temperature of the solution introduced into the crystallization vessel 1 via the supply line 2 is now increased. As can be seen from FIG. 3, the temperature of the solution within the crystallization vessel 1 also increases.
  • Dissolve ligands The temperature of the solution supplied is raised until the signal I of the scattered light probe 9 is within a tolerance range to the desired intensity Is. In other words, this means that the amount of the difference of the detected intensity I and the target intensity Is is smaller than a threshold value.
  • Limit value can be, for example, 1 0% of the target intensity Is.
  • the amount of the difference between the detected intensity I and the desired intensity Is is smaller than this limit value. If this is not the case, via the tempering device 7 and the control unit 10, the temperature of the solution, which is within the
  • Crystallization vessel 1 is still finely adjusted until the amount of this difference is within this limit.
  • Cooling crystallization process started.
  • the solution is controlled by the control unit 1 0, first cooled with a low cooling rate of about 3 K / h. After a certain time, i. For example, if a certain amount of crystals of a certain size is present, the cooling rate can be increased up to about 20 K / h. In this way, crystals of the ligand, one for the subsequent
  • the suspension with the crystals is then supplied by opening the valve 4 via the discharge line 3 of the separation unit 1 1, in which the suspension is filtered and the ligand of formula la2-3 can be obtained as a white solid.
  • FIG. 4 shows the relationship between the detected intensity I of the electromagnetic radiation scattered on the crystals and the temperature T, namely for the measured values shown in FIG.
  • the measured values in the arrow A show the dissolution of the crystals at the beginning of the process, ie before the actual crystallization process, and the measured values along the arrow K show the
  • the apparatus of the second embodiment comprises the apparatus of the first embodiment shown in Figure 1. Like parts are therefore designated by the same reference numerals. Reference will accordingly be made to the above description of these parts.
  • the device of the second embodiment shown in Figure 5 a further crystallization vessel V on.
  • the second crystallization vessel V comprises a feed line 2 ', a discharge line 3' with a valve 4 '. In the supply line 2 'are a
  • Temperature sensor 8 'and a further scattered light probe 9' is provided.
  • the valve 4 ', the tempering 5' and 7 ', the temperature sensors 6' and 8 'and the scattered light probe 9' are data technically coupled to the control unit 10.
  • an electronically controlled valve 16 is arranged in the supply line 2 for the first crystallization vessel 1, and the same is in the supply line 2 'for the second Crystallization vessel V an electronically controllable valve 17 is arranged.
  • the valves 16 and 17 are also coupled to the data from the control unit 10.
  • the device shown in FIG. 5 is operated as follows:
  • the solution is fed via the feed line 2 to the first crystallization vessel 1.
  • the valve 16 is opened and the valve 17 is closed, so no solution in the second
  • Crystallization vessel V passes.
  • the temperature is controlled as explained above, so that the temperature of the solution in the first crystallization vessel 1, when it is completely filled, the temperature value ⁇ associated with the target intensity ls, at which the desired amount of seed crystals is present.
  • valve 16 is closed and in the first crystallization vessel 1, the cooling crystallization begins, in which the temperature of the solution in the first crystallization vessel 1 is lowered.
  • Crystallization vessel 1 ' is supplied. By means of the tempering device 5 'and the temperature sensor 6' is then the temperature of the second
  • Scattering light probe 9 'measured intensity of the backscattered radiation of the target intensity ls approaches, as has already been described above for the first crystallization vessel 1.
  • the valve 17 is closed and in the second crystallization vessel 1 ', the cooling crystallization process is carried out as described above, in which the temperature of the solution is reduced crystals of the ligand form.
  • the crystallization process is carried out in the second crystallization vessel 1 ', the crystallization process in the first crystallization vessel 1 is completed and the valve 4 is opened, so that the suspension is fed via the discharge line 3 to the separation unit 11.
  • WO 2008/025852 A1 is described.
  • the ligand of the formula Ia2-3 is obtained, as has been described above with reference to FIGS. 1 to 5.
  • Another embodiment of the invention relates to a process for the preparation of isopulegol.
  • isopulegol is used as in
  • Yet another embodiment relates to a process for producing menthol.
  • isopulegol is prepared as described above.
  • Menthol is then prepared by hydrogenating the ethylenic double bond of the isopulegol thus obtained.

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  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

L'invention concerne un procédé pour la séparation d'une substance contenue dans une solution, dans lequel un rayon électromagnétique irradie la solution, une intensité du rayon électromagnétique qui a été diffracté par les cristaux se trouvant en solution est détectée, l'intensité détectée étant comparée à une intensité de consigne (IS) et la température de la solution étant ajustée en fonction de la différence entre l'intensité détectée et l'intensité de consigne (IS) de sorte que la valeur de cette différence diminue. Si la valeur de la différence entre l'intensité détectée et l'intensité de consigne (IS) est inférieure à une valeur limite, un procédé de cristallisation commence dans lequel les cristaux de la substance sont obtenus, lesquels sont ensuite séparés.
PCT/EP2015/055279 2014-03-19 2015-03-13 Procédé et dispositif pour la séparation d'une substance présente dans une solution WO2015140062A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
MX2016012125A MX2016012125A (es) 2014-03-19 2015-03-13 Procedimiento y dispositivo para separar una sustancia de una solucion.
JP2016557950A JP6702880B2 (ja) 2014-03-19 2015-03-13 溶液から物質を分離するための方法及びデバイス
ES15709501T ES2898659T3 (es) 2014-03-19 2015-03-13 Procedimiento para separar una sustancia de una solución
EP15709501.9A EP3119489B1 (fr) 2014-03-19 2015-03-13 Procédé de séparation d'une substance à partir d'une solution
PL15709501T PL3119489T3 (pl) 2014-03-19 2015-03-13 Sposób oddzielania substancji z roztworu
CN201580014534.2A CN106132496B (zh) 2014-03-19 2015-03-13 用于将物质从溶液中分离出来的方法和装置
EP21181477.7A EP3919148B1 (fr) 2014-03-19 2015-03-13 Dispositif de séparation d'une substance à partir d'une solution
US15/127,135 US10294182B2 (en) 2014-03-19 2015-03-13 Method and device for separating a substance out of a solution

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14160645.9 2014-03-19
EP14160645 2014-03-19

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WO2015140062A1 true WO2015140062A1 (fr) 2015-09-24

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EP (2) EP3119489B1 (fr)
JP (1) JP6702880B2 (fr)
CN (1) CN106132496B (fr)
ES (2) ES2981044T3 (fr)
MX (1) MX2016012125A (fr)
PL (1) PL3119489T3 (fr)
WO (1) WO2015140062A1 (fr)

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EP3919148C0 (fr) 2024-05-08
JP6702880B2 (ja) 2020-06-03
MX2016012125A (es) 2017-01-19
CN106132496B (zh) 2020-03-13
EP3919148B1 (fr) 2024-05-08
PL3119489T3 (pl) 2022-01-17
ES2981044T3 (es) 2024-10-07
EP3119489B1 (fr) 2021-08-25
US20170240494A1 (en) 2017-08-24
EP3119489A1 (fr) 2017-01-25
EP3919148A1 (fr) 2021-12-08
CN106132496A (zh) 2016-11-16
ES2898659T3 (es) 2022-03-08
JP2017512781A (ja) 2017-05-25
US10294182B2 (en) 2019-05-21

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